The present invention relates to sliver halide color photographic light sensitive materials and in particular to silver halide color photographic materials exhibiting enhanced sensitivity, superior color forming properties and improved storage stability.
In conventional silver halide color photographic materials (hereinafter, also denoted as color photographic materials or simply as photographic materials), a subtractive color system is employed and color images are formed by the combination of three dyes derived from yellow, magenta and cyan couplers.
As magenta couplers used in conventional color photographic materials are known 5-pyrazolone, pylazolinobenzoimidazole or indanone type couplers, and of these, 5-pyrazolone derivatives are broadly employed.
Substituents at the 3-position of the 5-pyrazolone ring of the 5-pyrazolone derivatives include, for example, an alkyl group, an aryl group, an alkoxy group described in U.S. Pat. Nos. 2,369,489 and 2,600,788, an acylamino group, and a ureido group described in U.S. Pat. No. 3,558,319. However, such couplers had the disadvantages that coupling activity with an oxidation product of a developing agent was so low that sufficiently high magenta dye image density could be obtained, the magenta dye images obtained through color development resulted in a relatively high secondary absorption in the blue light region and the longer wavelength-side absorption near edge of the main absorption was not sharp.
Further, 3-anilino-5-pyrazolone couplers described in U.S. Pat. Nos. 2,311,081, 3,677,764 and 3,684,514; British patent Nos. 956,261 and 1,173,513, exhibited a relatively high coupling activity, giving a high color density and having advantages such as unwanted absorption in the red light region being relatively low. However, commonly known 3-anilino-5-pyrazolone type couplers have disadvantages that solubility in organic solvents is relatively low and when a color photographic material containing this coupler is aged, precipitation of the coupler tends to easily occur in the photographic material. Furthermore, color photographic materials containing commonly known 3-anilino-5-pyrazolone couplers exhibited a disadvantage that the magenta dye image density, after being processed, varied after being aged.
In commercially available color photographic materials, as is well known, a coupler is not used alone but is used in combination with various functional couplers to improve image quality and color reproducibility. As such functional couplers, so-called DIR couplers and masking couplers (or colored couplers) are generally employed. However, in cases when the 3-anilino-5-pyrazolone coupler is used in combination with a functional coupler, it was shown that the foregoing disadvantages tended to increase.
Accordingly, it is an object of the present invention to provide a silver halide color photographic light sensitive material exhibiting enhanced sensitivity, superior color forming property and improved storage stability.
The above object of the invention can be accomplished by the following constitution:
(1) A silver halide color photographic light sensitive material comprising a support having thereon blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers, wherein at least one of the silver halide emulsion layers contains a coupler represented by the following formula (I): 
wherein R11 represents a secondary or tertiary alkyl group, or a cycloalkyl group; R12 represents an aryloxy group; R13 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R14 represents a halogen atom or an alkoxy group; R15, R16 and R17 independently represent a substituent; k1 is an integer of 0 to 5; m1 and n1 are each an integer of 0 to 4;
(2) The silver halide color photographic material described in (1) above, wherein the silver halide emulsion layer containing the coupler represented by formula (I) or another silver halide emulsion layer having the same color-sensitivity as the silver halide emulsion layer containing the coupler represented by formula (I) contains a compound represented by the following formula (II): 
wherein R21 and R24 represent a secondary or tertiary alkyl group, or a cycloalkyl group; R22 and R25 represent an aryloxy group; R23 and R26 represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R27 and R28 independently represent a substituent; m2 and n2 are each an integer of 0 to 4;
(3) The silver halide color photographic material described in (1) or (2) above, wherein the silver halide emulsion layer containing the coupler represented by formula (I) or another silver halide emulsion layer having the same color-sensitivity as the silver halide emulsion layer containing the coupler represented by formula (I) contains a compound represented by the following formula (III): 
wherein W represents a coupler moiety capable of forming a dye capable of being leached out of the photographic material upon reaction with an oxidation product of a color developing agent; TIME represents a timing group capable of releasing an inhibitor residue DI after being released from W upon reaction with an oxidation product of a color developing agent; and n3 is an integer of 0, 1 and 2;
(4) The silver halide color photographic material described in (1) or (2) above, wherein the silver halide emulsion layer containing the coupler represented by formula (I) or another silver halide emulsion layer having the same color-sensitivity as the silver halide emulsion layer containing the coupler represented by formula (I) contains a compound represented by the following formula (IV): 
wherein Y represents an yellow coupler moiety capable of forming an yellow dye upon reaction with an oxidation product of a color developing agent; TIME represents a timing group capable of releasing an inhibitor residue DI after being released from Y upon reaction with an oxidation product of a color developing agent; and n4 is an integer of 0, 1 and 2;
(5) The silver halide color photographic material described in any one of (1) through (4) above, wherein the silver halide emulsion layer containing the coupler represented by formula (I) or another silver halide emulsion layer having the same color-sensitivity as the silver halide emulsion layer containing the coupler represented by formula (I) contains a compound represented by the following formula (V): 
wherein R51 and R52 independently represent a secondary or tertiary alkyl group or a cycloalkyl group; R53 represents a halogen atom or an alkoxy group; R54 and R55 independently represent a substituent; k5 is an integer of 0 to 5; and m5 is an integer of 0 to 4.
The coupler (magenta coupler) represented by formula (I) will be described in detail.
In formula (I), R11, represents a secondary or tertiary alkyl group (e.g., i-propyl, sec-butyl, t-butyl, t-amyl, etc.) or a cycloalkyl group (e.g., cyclopropyl, cyclopentyl, cyclohexyl, etc.). The group represented by R11 may be substituted but unsubstituted one is preferred. The group represented by formula R11 preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Specifically preferred R11 is a secondary alkyl group and iso-propyl group is still more preferred. R12 represents an aryloxy group (e.g., phenoxy, naphthyloxy, etc.). The aryloxy group may be substituted by substituents and examples of the substituents include the following:
an alkyl group (e.g., t-amyl, t-octyl, dodcyl, etc), an cycloalkyl group (e.g., cyclopropyl, cyclhexyl, etc), an aryl (e.g., phenyl, naphthyl, etc), a heterocyclic group (e.g., 2-tetrahydrofuryl, 2-thiophenyl, 4-imidazolyl, indoline-1-yl, 2-pyridyl, etc), a carbonyl group (e.g., alkylcarbonyl such as acetyl, trifluoroacetyl and pivaloyl, and arylcarbonyl such as benzoyl, pentafluorobenzoyl and 3,5-di-t-butyl-4-hydroxybenzoyl), an oxycarbonyl group (e.g., alkoxycarbonyl such as methoxycarbonyl, cyclohexyloxycarbonyl and dedecyloxycarbonyl, aryloxycarbonyl such as phenoxycarbonyl, 2,4-di-t-amylphenoxycarbonyl and 1-naphthyloxycarbonyl, and heterocyclic-oxycarbonyl such as 2-pyridyloxycarbonyl and 1-phenylpyrazolyl-5-oxycarbonyl), a carbamoyl group (e.g., alkylcarbamoyl such as dimethylcarbamoyl and 4-(2,4-di-t-amylphenoxy)butylcarbonyl, and arylcarbamoyl such as 1-naphthylcarbamoyl), a sulfonyl group (e.g., alkylsulfonyl such as methanesulfonyl and trifluoromethanesulfonyl, and arylsulfonyl such as p-toluenesulfonyl), a sulfamoyl (e.g., alkylsulfamoyl such as dimethylsulfamoyl and 4-(2,4-di-t-amylphenoxy)butylaminosulfonyl, and arylsulfamoyl such as phenylsulfamoyl), a halogen atom, cyano group, nitro group, an alkenyl group (e.g., 2-propylene, oleyl, etc), hydroxy group, an alkoxy group (e.g., methoxy, 2-ethoxyethoxy, etc)an aryloxy group (e.g., phenoxy, 2,4-di-t-amylphenoxy, 4-(4-hydroxyphenylsulfonyl)phenoxy, etc), a heterocyclic-oxy group (e.g., 4-pyridyloxy, 2-hexahydropiranyloxy, etc), a carbonyloxy group (e.g., alkylcarbonyloxy such as acetyloxy, trifluoroacetyloxy and pivaloyloxy, and aryoxy such as benzoyloxy and pentfluorobenzoyloxy)a urethane group (e.g., alkylurethane such as N,N-dimethylurethane and arylurethane such as N-phenylurethane, N-(p-cyanophenyl)urethane), a sulfonyloxy group (e.g., alkylsulfonyoxy such as methanesulfonyloxy, trifluoromethanesulfonyloxy and dodecanesulfonyloxy and arylsulfonyloxy such as benzenesulfonyloxy and p-toluenesulfonyloxy), an amino group (e.g., alkylamino such as dimethylamino, cyclohexylamino and dodecylamino, and arylamino such as anilino and p-t-octylanilino), a sulfonylamino group (e.g., alkylsulfonylamino such as methanesulfonylamino, heptafluoropropanesulfonylamino and hexadecysulfonylamino, and arylsulfonylamino such as p-toluenesulfonylamino and pentafluorobenzenesulfonylamino), a sulfamoylamino group (e.g., alkylsulfamoylamino such as N,N-dimethylsulfamoylamino and arylsulfamoylamino such as N-phenylsulfamoylamino), an acylamino group (e.g., alkylcarbonylamino such as acetylamino and myrystylamino and arylcarbonylamino such as benzoylamino), a ureido group (e.g., alkylureido such as N,N-dimethylureido, and arylureido such as N-phenylureido and N-(p-cyanophenyl)ureido), an alkylthio group (e.g., methylthio, t-octylthio, etc), an arylthio group (e.g., phenylthio, etc), and a heterocycli-thio group (e.g., 1-phenyltetrazole-5-thio, 5-methyl-1,3,4-oxazole-2-thio, etc).
Of the groups represented by R12 is preferred a phenoxy group having a substituent on the benzene ring, i.e., a substituted phenoxy. The substituent is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a halogen atom and an alkoxycarbonyl group. The total carbon number of the substituent(s) on the benzene ring is preferably 4 to 20 and more preferably 8 to 12.
R13 represents a hydrogen atom, a cycloalkyl group, an aryl-group or a heterocyclic group, of which a hydrogen atom is preferred. R14 represents a halogen atom (e.g., chlorine, bromine, iodine, etc.) or a alkoxy group (e.g., methoxy, I-propoxy, etc.), of which R14 is preferably a chlorine atom or methoxy group. R15 represents a substituent. Any group capable of being substituted on a benzene ring may be included and exemplary examples thereof are the same as cited as the substituents for R12. R15 is prefrerably a halogen atom and a chlorine atom is specifically preferred. Specifically, three chlorine atoms being substituted at the 2, 4, 6-position is preferred.
R16 also represents a substituent. Any group capable of being substituted on a benzene ring may be included and exemplary examples thereof are the same as cited as the substituents for R12. R16 is prefrerably an acylamino group, an oxycarbonyl group, carbamoyl group, sulfonyl group and sulfamoyl group. R17 also represents a substituent. Any group capable of being substituted on a benzene ring may be included and exemplary examples thereof are the same as cited as the substituents for R12. R15 is prefrerably a halogen atom.
Representative examples of the coupler represented by formula (I) are shown below but are not limited to these examples. 
The compound represented by formula (II) will be described. In formula (II), R21 and R24 independently represent a secondary or tertiary alkyl group or a cycloalkyl group and exemplary examples thereof are the same as cited as R11 of formula (I). R22 and R25 each represent an aryloxy group and exemplary examples thereof are the same as cited as R12 of formula (I). R23 and R26 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and exemplary examples thereof are the same as cited as R13 of formula (I). R27 and R28 each represent a substituent and exemplary examples thereof are the same as cited as R17 of formula (I). In formula (II), two xe2x80x94NHCO groups may be substituted on any position of each benzene ring and substitution at the ortho-position for the sulfur atom is preferred.
Representative examples of the compound represented by formula (II) are shown below, but are by no means limited to these examples. 
Next, the compound represented by formula (III) will be described. The compounds represented by formula (III) are a so-called leachable decoloring DIR coupler, as described in JP-A Nos. 58-160954, 63-37350, 4-356042, 5-61160 (hereinafter, the term, JP-A means an unexamined published Japanese Patent Application); and U.S. Pat. No. 4,482,629.
In formula (III), the coupler moiety represented by W may be any coupler moiety having the same property as described above, and is preferably a 1-naphthol substituted at the 2-position by an unsubstituted carbamoyl group or an alkylcarbamoyl group substituted with a water-solubilizing group (e.g., carboxy, sulfo, hydroxy, methoxycarbonyl, ethoxycarbonyl, etc.), in terms of higher reactivity and superior leachability.
The group represented by TIME is a so-called timing group and a linkage group used for the purpose of adjustment of the coupling reaction rate of the compound of formula (III) and an oxidation product of a color developing agent, and of the releasing rate of the inhibitor residue represented by DI. Representative timing groups are described in U.S. Pat. Nos. 4,861,701, 4,248,962, 4,409,323, 4,482,629 and 4,857,447.
The inhibitor residue represented by DI refers to a compound having a function of retarding the developing rate in the color developing process, that is, a group in which a hydrogen atom is removed from the inhibitor. Exemplary inhibitors include mercaptotetrazoles, mercaptobenzothiazoles, mercaptobenzoxazoles, mercaptobenzimidazoles, mercpatooxadiazoles, mercaptothiadiazoles, benzoriazoles, and 1,2,3- or 1,2,4-triazoles. From the viewpoint of reduction in contamination of processing solutions, the DI is preferably a compound inhibiting development at the time of being released from the active position of the coupler upon color development reaction, which is decomposed to a compound substantially having no photographic effect, after being leached into a color developing solution. The compound releasing the DI exhibiting such properties is a so-called deactivation type DIR coupler. The deactivation type DIR coupler is systematically defined in JP-A 57-151944, and exemplary compounds are described in JP-A Nos. 58-205150, 60-218644, 60-221750, 60-233650, 61-11743, 2-48655, 3-18844, 3-228048, 4-211245, 4-308842; and U.S. Pat. No. 4,782,012.
The compounds represented by formula (III) can be synthesized with reference to the methods described in the above-cited patents. Exemplary examples of the compound of formula (III) are shown below, but are by no means limited to these examples. 
The compound represented by formula )IV) will be described below. In formula (IV), Y represents a coupler moiety capable of forming a yellow dye upon reaction with an oxidation product of a color developing agent in the color development process. Representative yellow dye forming couplers are described in U.S. Pat. Nos. 2,875,057, 2,407,210, 3,265,506, 2,298,433, 3,048,194, 3,447,928; and xe2x80x9cFarbkuppler eine Literturiebersichtxe2x80x9d (Affa Mitteilungen, Vol. III page 112-126, 1961). Preferred Y is acyacetoamides such as pivaloylacetoanilides and benzoylacetoanilides. TIME represent a timing group capable of releasing the DI after being released from Y upon reaction with an oxidation product of a color developing agent, and examples thereof are the same as cited as TIME and DI of formula (III).
The compounds represented by formula (IV) can be synthesized with reference to the methods described in the above-cited patents. Exemplary examples of the compound of formula (IV) are shown below, but are by no means limited to these examples. 
The compound represented by formula (V) will be described below. The compound represented by formula (V) is a so-called masking coupler or colored coupler, which is yellow-colored.
In formula (V), R51 and R52 represent a secondary or tertiary alkyl group (e.g., i0propyl, sec-butyl, t-butyl, t-amyl, etc.) or a cycloalkyl group (e.g., cyclopropyl, cyclopentyl, cyclohexyl, etc.). R51 and R52 is preferably a secondary or tertiary alky group having 6 or less carbon atoms or a cycloalkyl group, and i-propyl or sec-butyl are specifically preferred. R53 represents a halogen atom (e.g., chlorine, fluorine, etc.) or an alkoxy group (e.g., methoxy, I-propoxy, etc.). R53 is preferably a chlorine atom or methoxy group. R54 represents a substituent. The substituent may be any group capable of being substituted on a benzene ring and examples thereof are the same as cited as substituent for R12 of formula (I). R54 is preferably an acylamino group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group. R55 also represents a substituent. The substituent may be any group capable of being substituted on a benzene ring and examples thereof are the same as cited as substituent for R12 of formula (I). R55 is preferably a halogen atom.
The compounds represented by formula (V) can be synthesized with reference to the method described in JP-A 62-50830. Exemplary examples of the compound of formula (V) are shown below but are by no means limited to these examples. 
Next, exemplary synthesis of the compound represented by formulas (I) or (II) is described below.